Metastable Phase Formation in Electrodeposited Co-Rich Co-Cu and Co-Ni Alloys

In a previous work [El-Tahawy et al., J. Magn. Magn. Mater. 560, 169660 (2022)], we reported that from a sulfate type bath, hcp-Co can be electrodeposited at high pH and low current density and investigated the structure and magnetoresistance (MR) characteristics of such hcp-Co electrodeposits. Based on this earlier work, Co-rich Co-Cu and Co-Ni alloy electrodeposits were prepared under the same conditions by adding varying amounts of CuSO4 and NiSO4, respectively, to the CoSO4 bath. According to the results of detailed structural studies by various X-ray diffraction (XRD) geometries, in both the Co-Cu and Co-Ni systems an hcp phase formed exclusively up to about 2 at% of the alloying element. Above this concentration, a significant fcc phase fraction appeared in Co-Cu and a minor fcc fraction in Co-Ni up to about 8 at%. This means that the destabilization effect of Cu on hcp-Co is higher than that of Ni. Although the reduction of the stability of hcp-Co with increasing Cu and Ni content is a well-known phenomenon, a quantitative comparison of this effect in Co-Cu and Co-Ni alloys is missing from the literature. The measured lattice constants are analyzed in comparison with Vegard's law for the Co-Cu and Co-Ni element pairs deduced from data previously reported for the hcp and fcc phases of all three pure elements. For Co-rich Co-Ni alloys, the concentration dependence of the lattice parameters was found to follow Vegard's law for both the hcp and fcc phases due to the miscibility of the two components. For the Co-rich Co-Cu alloys, the data indicate a positive deviation from Vegard's law for both the hcp and fcc phases in agreement with the known similar behavior of fcc Co-Cu alloys for the whole composition range. The positive deviation from Vegard's law in the Co-Cu system is due to the excess mixing volume required for solid solution alloy formation of these immiscible elements in either phases. The MR data are discussed in the light of the observed phases and of the MR parameters reported in our previous work on the hcp and fcc phases of pure Co.